JPS63152665A - Filler-incorporated thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in mechanical strength, heat resistance, etc., suitable for automobile parts, domestic appliance parts, etc., by incorporating a thermoplastic resin with filler in the presence of a specific amine polymer. CONSTITUTION:The objective composition comprising (A) 95-40wt.% of a thermoplastic resin (pref., polyolefin resin and/or polyamide resin), (B) 5-60wt.% of filler (e.g., mica, glass), and (C) such an amount of an unsaturated amine homopolymer (acid salt) (e.g. polyallylamine) as to be >=0.1(pref. <=5)pt.wt. based on 100pts.wt. of the filler B. The filler B which has been surface-treated with the component C in advance shall be blended in the component A.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a thermoplastic resin composition containing a filler, and more specifically, a thermoplastic resin composition containing a thermoplastic resin, a filler, and an unsaturated amine homopolymer or an acid salt thereof as essential components. The present invention relates to a resin composition having excellent mechanical strength, heat resistance, etc.

(Prior art) Thermoplastic resins have a wide range of uses, including automotive parts and household electrical appliances, and can be mixed with inorganic or organic fillers to improve mechanical strength, heat resistance, and flame retardancy. It is widely practiced to achieve effects such as adding or increasing the amount of filler, and there are various types of fillers. However, when compounding fillers, the dispersibility may be poor due to the low affinity with the thermoplastic resin at the dispersed interface depending on the material, and the filler compounding effect may not be fully demonstrated. Surface treatments and other methods are often used to improve the affinity between both interfaces. For example, surface treatments include fatty acids and their metal salts, acid amides,
A method is known in which the surface of the filler is treated in advance using resin acids, various coupling agents, wax, oil, etc.

When mixing hydrophilic fillers, mainly inorganic materials, with hydrophobic thermoplastic resins such as polyolefins, it is especially necessary to improve this affinity, and the surface treatment agents are usually silane-based, titanium-based, or A so-called coupling agent such as an aluminum-based coupling agent is used. Another method is to mix a polyolefin modified with maleic anhydride or acrylic acid with a thermoplastic resin (Japanese Patent Publication No. 51-10265, Japanese Unexamined Patent Publication No. 56-14945).
Publication No. 2) or a combination of both of the above methods (Special Publication No. 45-3)
6421, Japanese Unexamined Patent Publication No. 55-40719), etc. are known. Some methods of surface-treating fillers with substances containing amino groups are also known, such as an example using an alkylamine monomer (Japanese Patent Application Laid-Open No. 14751-1983).
Publication No.). Polymers such as polyolefins modified with functional groups including amino groups are also known (Japanese Unexamined Patent Publication Nos. 49-13244 and 50-95346); No disclosure has been made.

As mentioned above, the performance of the conventionally used methods is still insufficient, and in order to obtain the effect of improving mechanical strength, heat resistance, etc., the required amount of addition is large (and therefore, the composition Various problems remain, such as deterioration of other properties of the filler and increased cost, and there is a desire to develop technology that more effectively improves the affinity between the filler and thermoplastic resin. .

(Problems to be Solved by the Invention) The present invention improves the above-mentioned drawbacks by improving the affinity between the thermoplastic resin and the filling material, and by using new additives, it has excellent mechanical strength and heat resistance. The object of the present invention is to provide an inexpensive thermoplastic resin composition containing a filler.

(Means for Solving the Problem) As a result of intensive studies in line with the above objectives, the present inventors found that
It has been discovered that a thermoplastic resin composition with improved properties can be obtained by using a specific amine-based polymer as an additive when mixing a filler with a thermoplastic resin! Based on this, we have arrived at the present invention.

That is, the present invention provides a thermoplastic resin composition containing a thermoplastic resin, a filler, and an unsaturated amine homopolymer or an acid salt thereof as essential components.

Thermoplastic resins used in the present invention include polyolefin resins, polyamide resins, polyvinylidene chloride resins, saponified products of ethylene-vinyl acetate copolymers, polyester resins, polyacetal resins, polystyrene resins, ABS resins, and polycarbonates. resin, polyvinyl alcohol resin, fluorine resin, polyphenylene oxide resin, polyphenylene sulfide resin, polyether/etherketone resin 11L polyether sulfone resin, polyamideimide resin, polyimide resin, polyacetal resin, polysulfone@resin, polyarylate resin,
Examples include polyetherimide resin and polyparabanic acid resin. Particularly preferred thermoplastic resins for use in the present invention are the above-mentioned polyolefin resins, polyamide resins, or a mixture of both.

Various polymers are used as polyolefin resins due to their excellent water resistance, chemical resistance, and electrical properties, such as ethylene, propylene, butene-1,4-methyl-pentene-1, hexene-1, and octene. -1 and other copolymers; copolymers of ethylene and vinyl esters such as ethylene and vinyl acetate copolymers; ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-ethyl acrylate copolymers; polymers, ethylene biounsaturated carboxylic acids such as ethylene-ethyl methacrylate copolymers,
Examples include copolymers with unsaturated carboxylic pre-esters and mixtures thereof.

Polyamide resins are used because they have excellent abrasion resistance, lubricity, oil resistance, etc., and include various types of nylon.

The filter fillers used in the present invention include inorganic and organic fillers. Inorganic fillers include calcium carbonate, talc, silica, clay, kaolin, alumina, aluminum hydroxide, magnesia, magnesium hydroxide, calcium sulfate, calcium sulfite, barium sulfate, aluminum silicate, calcium silicate, sodium silicate, Potassium silicate, magnesium carbonate, calcium oxide, titanium oxide, mica, glass flakes, zeolite,
Examples include diatomaceous earth, perlite, vermiculite, shirasu balloons, glass microballoons, fly ash, and glass peas.

On the other hand, examples of organic fillers include wood flour, pulp powder, and powder of phenolic resin and other synthetic resins.

Among these fillers, preferred in the present invention are hydrophilic substances, mainly inorganic substances, such as those containing one or more of silicates, carbonates, and sulfates, especially mica, talc, glass, calcium silicate,
Silicate-based materials such as white earth are preferred. Among these, mica and powdered or fibrous glass are most desirable.

The average particle size of the filler varies depending on the application, but it is usually 5.
~500 μl is used.

The third component used together with the thermoplastic resin and filler in the present invention is an unsaturated amine homopolymer or its acid salt (hereinafter abbreviated as amine polymer). Specific examples of unsaturated amines include vinylamine, allylamine, allylmethylamine, allyldimethylamine, 1-amino-4
Examples include aliphatic olefinic amines such as -pentene and aromatic olefinic amines such as aminostyrene or styrene nuclear substituted with an aminoalkyl group. Among these olefinic amines, aliphatic olefinic amines are preferred, and allylamine is particularly preferred.

The type of amine is preferably a primary amine from the viewpoint of reactivity. Furthermore, since the inorganic acid salt of the unsaturated amine homopolymer becomes a water-soluble polycation, it is advantageous when used as an aqueous solution for surface treatment of fillers.

The degree of polymerization of the above-mentioned amine-based polymer is not particularly limited, depending on its type, but in the case of allylamine homopolymer (hereinafter referred to as polyplylamine) or its salts, it is 50%. ~1.000 is used, and among these, 500 or less is preferred. In the present invention, the homopolymer of an unsaturated amine refers to one in which the main part of the repeating units constituting the polymer is formed by the above-mentioned polymerizable unsaturated amine. Therefore, copolymers of unsaturated amines and copolymers with small amounts of other components that do not substantially impair their properties are also included.

The blending ratio of each component in the filler-containing thermoplastic resin composition of the present invention is 95 to 40% by weight of the thermoplastic resin, with the total weight of the thermoplastic resin and filler being 100% by weight.
, preferably 80 to 60% by weight, and 5 to 60% by weight, preferably 20 to 40% by weight. Also, assuming that the amount of filler is 100 parts by weight, the amount of amine polymer is 0.
The amount is 1 part by weight or more, preferably 5 parts by weight.

If the content of the filler is less than 5% by weight, no improvement in mechanical strength and heat resistance will be seen, while if it exceeds 60% by weight, the characteristics of the thermoplastic resin will decrease and it will no longer be possible to use it for its original purpose. I also don't like it. When the amount of the amine polymer is less than 1 part by weight, no effect is observed.

In the present invention, any method can be selected to produce the filler-containing thermoplastic resin composition.

For example, after surface-treating the filler with an amine polymer, the resulting treatment product may be mixed with a thermoplastic resin, or after adding and mixing the amine polymer to the thermoplastic resin, the filler may be may be mixed. Alternatively, the three components can be blended and mixed from the beginning. However, in order to maximize the dispersion effect of the filler and its adhesion to the thermoplastic resin by using as little amount of the amine polymer as possible, it is preferable to surface-treat the filler in advance.

The surface treatment method usually involves dissolving or dispersing an amine polymer in a liquid, adding a predetermined amount of filler to the solution or dispersion, and stirring at high speed to thoroughly coat the surface of the filler with the amine polymer. A method of contacting the target is used. If necessary, the liquid is removed by evaporation and the surface-treated filling material is recovered in a dry state.

To mix the surface-treated filler with the thermoplastic resin, both components are blended in a predetermined ratio, mixed for 4 m using a Henschel mixer, etc., and then melt-kneaded using an open roll, Banbury mixer, or pressure kneader. do. However, these are generally batch operations and have poor productivity, so a method using an extruder is preferred. As the extruder, a full-flight screw extruder may be used, but since crosstalk may be insufficient, it is preferable to use an extruder with a kneading mechanism or a multi-screw extruder.

In addition to the above three components, other components such as antioxidants, heat stabilizers, weathering agents, dyes or pigments, antistatic agents, lubricants, mold release agents, plasticizers, etc. may be used as long as they do not impair the purpose of the present invention. Agents or deodorizing agents can be added. The above additives may be used in combination.

(Effects of the Invention) The resin composition of the present invention improves tensile strength, bending strength, and Both elastic modulus and heat resistance are greatly improved. Since thermoplastic resins with excellent mechanical strength and heat resistance can be obtained from relatively inexpensive materials, they are used in various automobile parts, various household appliance parts, electronic parts, mechanical parts, general miscellaneous goods, etc. It is expected to be used in a wide range of fields.

(Examples and Comparative Examples) The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited by these. Note that the physical property values of the test pieces were measured by the following method.

Tensile yield strength: JIS K67S8 (K711B)
Bending strength: JIS K8758tK7203)
Flexural modulus j JIS K675g (K7203)
Deflection temperature under load: JIS K7207 Bending stress shall be as follows depending on the type of thermoplastic resin: 衷JL-LヱA The following were used as the thermoplastic resin, filler, and amine polymer.

Thermoplastic resin: (A) Crystalline polypropylene (melt fluorate 8.0g/10sain; product name: Nisseki Polypro J150G, Nippon Petrochemical 1ff) Filler: (C-1) Gold mica (average particle size 9oμ product name) Nisshilite Mica 200H
(manufactured by Kuraray) Amine polymer: (D-1) Polyallylamine hydrochloride (1) (solid, degree of polymerization 80-12oH Product name: P A A-HC1-33
, Nittobo vRHM) was dissolved in water and used as an aqueous solution with a concentration of 10%.

(D-2) Polyallylamine hydrochloride (2) (50% aqueous solution, degree of polymerization 8O-12o; Trade name: PAA-HC1-
(3L, manufactured by Nitto Boseki ■) was diluted with water and used as an aqueous solution with a concentration of 10% by weight.

(D-3) Polyallylamine hydrochloride (3) (40% aqueous solution, degree of polymerization 540-900; Trade name: PAA-HCI
-1OL, manufactured by Nitto Boseki Jun) was diluted with water and used as an 8% by weight aqueous solution.

In Examples 1 to 4, the surface of the filler was treated with an amine polymer. That is, while gold mica was heated in a Henschel mixer (730 rpm), the above three types of aqueous solutions were added for 5 times each so that the amount of polyallylamine hydrochloride was a predetermined amount per 100 parts of Heleica in the mixer. After the addition was completed, the mica was continued to be mixed for another 5 ml, and after stopping, the wet mica was taken out of the mixer and spread evenly on a shallow tray.
It was dried at 130°C.

Mica surface-treated in this way is blended with crystalline polypropylene in a predetermined ratio, and then mixed with Henshi Z Lumixer.
(730 rpm) for 35 h, melt mixing and strand extrusion were performed at 230° C. using a single-screw kneading extruder, and pellets were produced using a tablet machine. Using this, a test piece was prepared by injection molding, and the physical properties were measured. The composition and measurement results are shown in Table 1.

Spoon J! JLu Compositions were produced in the same manner as in Examples 1 to 4 except that the amine polymer was not used, and the physical properties were measured. The results are shown in Table 1.

Compositions were prepared in the same manner as in Examples 1 to 4, except that the following silane coupling agent was used as a surface treatment agent.

Silane coupling agent: (E) γ-(2-aminoethyl)aminopropyltrimethoxysilane (trade name: 5H6020, manufactured by Le Silicone ■) Water was added to form an aqueous solution with a concentration of 20% by weight.

The composition and physical property measurement results are shown in Table 1.

Example 5 The same procedure as Example 2 was carried out except that the blending ratio of the thermoplastic resin and the filler was changed. The composition and physical property measurement results are shown in Table 1.

A composition was prepared in the same manner as in Example 5 except that the mosquito-repellent-Uamine-based polymer was not used, and the physical properties were measured. The results are shown in Table 1.

The process was carried out in exactly the same manner as in Example 2, except that the following mica was used as the filler. The results are shown in Table 1.

Filler: (C-2) White mica (average particle size 18μsB, trade name: 400W, manufactured by Kuraray) The composition was treated in the same manner as in Example 6, except that the 5-5 amine polymer was not used. It was manufactured and its physical properties were measured. The results are shown in Table 1.

Example 7 The same procedure as in Example 2 was carried out except that the following nylon was used as the thermoplastic resin. The results are shown in Table 1.

Thermoplastic resin: (B) Nylon-6 (Product name: Toshi Amilan CM1041. Manufactured by Toshi ■) Comparative Example 5 A composition was produced by processing in the same manner as in Example 7 except that the amine polymer was not used. Then, the physical property values were measured. The results are shown in Table 1.

Reference Example A composition was produced in exactly the same manner as in Comparative Example 2, except that the following modified thermoplastic resin was added to the thermoplastic resin. The composition and physical property measurement results are shown in Table 1.

Modified thermoplastic resin; (F) Acrylic acid modified polypropylene (acrylic acid content 6%; trade name: Dexon PB10
01. As is clear from the results in Table 1 (manufactured by Exxon Chemical Co., Ltd.), the thermoplastic resin compositions containing fillers of Examples 1 to 7, which are within the scope of the present invention, are all mechanically resistant by using a small amount of amine polymer. It showed excellent physical strength and heat resistance. On the other hand, Comparative Examples 1 to 1 which are outside the scope of the present invention
5 shows that it is difficult to maintain the above performance in a well-balanced manner.

Claims (9)

[Claims] (1) A filler-containing thermoplastic resin composition containing a thermoplastic resin, a filler, and an unsaturated amine homopolymer or an acid salt thereof as essential components. (2) The total amount of the thermoplastic resin and filler is 10
Assuming 0% by weight, the amount of thermoplastic resin is 95-40% by weight
The filler-containing thermoplastic resin composition according to claim 1, wherein the amount of the filler is 5 to 60% by weight. (3) The filler-containing thermoplastic resin according to claim 1, wherein the amount of the unsaturated amine homopolymer or its acid salt is 0.1 part by weight or more based on 100 parts by weight of the filler. Composition. (4) The filler-containing thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is a polyolefin polymer and/or a polyamide polymer. (5) Claim 1, wherein the filler is an inorganic substance.
A thermoplastic resin composition containing a filler as described in 1. (6) The filler-containing thermoplastic resin composition according to claim 5, wherein the inorganic filler is mica or glass. (7) The filler-containing thermoplastic resin composition according to claim 1, wherein the unsaturated amine is an olefinic amine. (8) The filler-containing thermoplastic resin composition according to claim 1, wherein the unsaturated amine homopolymer is polyallylamine. (9) The filler-containing thermoplastic resin composition according to claim 1, which is obtained by mixing a filler whose surface has been previously treated with the unsaturated amine homopolymer or its acid salt with a thermoplastic resin.